DE902011C - Process for the production of unsaturated compounds containing sulfur - Google Patents
Process for the production of unsaturated compounds containing sulfurInfo
- Publication number
- DE902011C DE902011C DEC1709D DEC0001709D DE902011C DE 902011 C DE902011 C DE 902011C DE C1709 D DEC1709 D DE C1709D DE C0001709 D DEC0001709 D DE C0001709D DE 902011 C DE902011 C DE 902011C
- Authority
- DE
- Germany
- Prior art keywords
- parts
- unsaturated compounds
- production
- compounds containing
- containing sulfur
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
- C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/02—Thiols having mercapto groups bound to acyclic carbon atoms
- C07C321/04—Thiols having mercapto groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/12—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms
- C07C321/14—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von schwefelhaltigen ungesättigten Verbindungen Es ist bereits bekannt, daß sich Mercaptane in Gegenwart von Katalysatoren, insbesondere basisch wirkenden Stoffen, an Acetylen unter Bildung von Thiovinyläthern und bzw. oder Äthandithioäthern oder beiden anlagern lassen.Process for the preparation of unsaturated compounds containing sulfur It is already known that mercaptans in the presence of catalysts, in particular basic substances, acetylene with the formation of thiovinyl ethers and resp. or ethandithioethers or both.
Es wurde nun gefunden, daß sich bei organischen Aminen, die zwei dreifache Kohlenstoff-Kohlenstoff-Bindungen enthalten, Mercaptane besonders leicht an eine der Dreifachbindungen anlagern lassen.It has now been found that with organic amines, the two threefold Containing carbon-carbon bonds, mercaptans are particularly easy to attach to one of the triple bonds can attach.
Die Mitverwendung von Katalysatoren ist im allgemeinen nicht erforderlich, doch kann die Umsetzung durch basisch wirkende Stoffe oder Schwermetalle, wie Quecksilber, Silber oder Kupfer oder deren Verbindungen, oder auch durch Einwirkung von Licht beschleunigt werden. Die Umsetzungstemperatur liegt meist unter ioo°, kann aber auch in einzelnen Fällen, besonders bei der Mitverwendung von Lösungs-und Verdünnungsmitteln, darüber liegen.The use of catalysts is generally not necessary, but the reaction can be caused by basic substances or heavy metals such as mercury, Silver or copper or their compounds, or through the action of light be accelerated. The reaction temperature is usually below 100 °, but can also in individual cases, especially when using solvents and thinners, lie above.
Geeignete Ausgangsstoffe sind beispielsweise Dialkylaminopentadiine, Tetraalkyldiaminohexadiine, Dialkylaminohexadiinole, wie i-Dialkylamino-6, 6-dimethyl-hexadiin-2, q.-ol-6, sowie die i-Dialkylamino-6-methyl-8-nitrilo-octadiin-2, 4-ole-6 und die entsprechenden Carbonsäuren und ihre funktionellen Abkömmlinge.Suitable starting materials are, for example, dialkylaminopentadiines, Tetraalkyldiaminohexadiynes, dialkylaminohexadiinols, such as i-dialkylamino-6, 6-dimethylhexadiyne-2, q.-ol-6, as well as the i-dialkylamino-6-methyl-8-nitrilo-octadiyne-2, 4-ole-6 and the corresponding carboxylic acids and their functional derivatives.
Als Mercaptane kommen Methyl-, Äthyl-, Oxäthyl-, Butyl- und Benzylmercaptan, ferner Thiophenole, Thiokresole, Thionaphthole, Mercaptocarbonsäuren, wie Mercaptobuttersäure, und deren Abkömmlinge in Betracht.The mercaptans are methyl, ethyl, oxethyl, butyl and benzyl mercaptan, also thiophenols, thiocresols, thionaphthols, mercaptocarboxylic acids, how Mercaptobutyric acid and its derivatives.
Die neuen schwefelhaltigen ungesättigten Verbindungen sind wertvolle Zwischenerzeugnisse.The new sulfur-containing unsaturated compounds are valuable Intermediate products.
Es ist zwar bekannt, Mercaptane an. organische Amine mit einer Dreifachbindung anzulagern (vgl. die USA.-Patentschrift 2 11g 8o2). Es war jedoch nicht zu erwarten, daß organische Amine mit zwei Dreifachbindungen in der Weise reagieren, daß nur i Mol der Mercaptane an nur eine der Dreifachbindungen angelagert wird, während die andere Dreifachbindung, selbst bei Anwendung eines Überschusses an Mercaptan, unverändert bleibt.Although it is known to use mercaptans. organic amines with a triple bond to be deposited (cf. US Pat. No. 2 11g 8o2). However, it was not to be expected that organic amines with two triple bonds react in such a way that only i mole of the mercaptans is attached to only one of the triple bonds, while the other triple bond, even when using an excess of mercaptan, remains unchanged.
Die in den folgenden Beispielen angegebenen Teile sind Gewichtsteile. Beispiel i In ein Gemisch aus 25 Teilen 5-Diäthylamino-pentadiin-i, 3 und 4o Teilen Methanol läßt man bei 50° unter Rühren im Laufe einer Stunde 23 Teile Benzylmercaptan fließen. Dann treibt man das Methanol ab und destilliert den Rückstand unter vermindertem Druck. Man erhält ein hellgelbes, beim Stehen rot werdendes Öl der Zusammensetzung C1oH21NS in einer Ausbeute von 75 % der für die Anlagerung von i Mol Mercaptan berechneten Menge (Kpi = z61°). Beispiel 2 In eine Lösung von 22 Teilen i, 6-Bis-diäthylaminohexadün-2, 4 (= o,= Mol) und 2,5 Teilen Kaliumhydroxyd in 4o Teilen Methanol läßt man bei 65' unter Rühren 25 Teile Benzylmercaptan (= o,2 Mol) einfließen. Dann läßt man abkühlen, neutralisiert mit der berechneten Menge Essigsäure und wäscht mit Wasser aus. Die Ölschicht wird nach dem Trocknen destilliert. Man erhält etwa io Teile unverändertes Benzylmercaptan zurück und als Umsetzungserzeugnis in einer Ausbeute von 66 % der berechneten Menge eine Verbindung C21 H32 N2 S, die Anlagerungsverbindung von i Mo1 Benzylmercaptan an i Mol des Hexadiins, (Kpo,5 = 175 bis 178°) als schwachgelbes Öl. Beispiel 3 In eine Lösung von 43 Teilen Oxäthylmercaptan in 5o Teilen Methanol läßt man bei 40° unter Rühren 68 Teile 5-Diäthylamino-pentadiin-i, 3 einfließen und erhitzt das Gemisch noch kurze Zeit auf 50°. Bei der Destillation des Umsetzungsgemisches erhält man nach der Entfernung des Methanols 89 Teile einer Verbindung (Kpo,oi = 125 bis r3o°, Dichte: 1,o37), der nach der Analyse die Formel C"H"0NS zukommt. Sie ist durch Addition der Ausgangsstoffe im Molverhältnis i : i entstanden. Beispiel 4 . In eine Lösung von Zoo Teilen ß-Mercaptobuttersäure-n-butyl-ester in 5o Teilen Methanol läßt man bei So' unter Rühren 68 Teile 5-Diäthylamino-pentadiin-i, 3 einfließen und erhitzt das Gemisch noch kurze Zeit auf 8o°. Bei der Destillation des Umsetzungsgemisches im Hochvacuum erhält man neben wenig unverändertem Ausgangsstoff 85 Teile einer Verbindung (Kpo,oi = 135 bis 1q.2°), die nach der Analyse durch Anlagerung von i Mol der Mercaptoverbindung an i Mol des Pentadiins entstanden ist. Beispiel 5 Eine Mischung von 68 Teilen 5-Diäthylamino-pentadün-i, 3, 5o Teilen Tetrahydrofuran und 7o Teilen ß-Mercaptobuttersäuremethylester wird einige Zeit auf 5o° und dann auf 7o bis 8o° erhitzt. Im Wasserstrahlvacuum treibt man dann das Tetrahydrofuran und nicht umgesetzte Ausgangsstoffe ab. Der Rückstand wird im Hochvacuum destilliert. Man erhält 75 Teile eines Aminothioäthers der Zusammensetzung (#14H2302NS (Kpo,o1 = io4 bis io6°, D1° = i,oig8), der durch Anlagerung von i Mol der Mercaptoverbindung an i Mol des Diins entstanden ist.The parts given in the following examples are parts by weight. Example i 23 parts of benzyl mercaptan are allowed to flow into a mixture of 25 parts of 5-diethylaminopentadiyne-i, 3 and 40 parts of methanol at 50 ° with stirring over the course of one hour. The methanol is then driven off and the residue is distilled under reduced pressure. A light yellow oil of the composition C1oH21NS, which turns red on standing, is obtained in a yield of 75% of the amount calculated for the addition of 1 mol of mercaptan (Kpi = z61 °). Example 2 In a solution of 22 parts of i, 6-bis-2-diäthylaminohexadün in 4o parts of methanol is allowed at 65 ', 4 (= o = mol) and 2.5 parts of potassium hydroxide with stirring 25 parts of benzyl mercaptan (= o, 2 moles). It is then allowed to cool, neutralized with the calculated amount of acetic acid and washed out with water. The oil layer is distilled after drying. About 10 parts of unchanged benzyl mercaptan are obtained back and, as a reaction product in a yield of 66% of the calculated amount, a compound C21 H32 N2 S, the addition compound of 1 mol of benzyl mercaptan with 1 mol of hexadiyne, (Kpo, 5 = 175 to 178 °) as pale yellow oil. EXAMPLE 3 68 parts of 5-diethylamino-pentadiyne-1,3 are allowed to flow into a solution of 43 parts of oxethyl mercaptan in 50 parts of methanol at 40 ° with stirring, and the mixture is heated to 50 ° for a short time. In the distillation of the reaction mixture, after removal of the methanol, 89 parts of a compound (Kpo, oi = 125 to r30 °, density: 1.037) are obtained which, according to the analysis, has the formula C "H" 0NS. It was created by adding the starting materials in the molar ratio i: i. Example 4. 68 parts of 5-diethylamino-pentadiyne-1,3 are allowed to flow into a solution of zoo parts of β-mercaptobutyric acid n-butyl ester in 50 parts of methanol at So 'with stirring and the mixture is heated to 80 ° for a short time. Distillation of the reaction mixture in a high vacuum gives, in addition to little unchanged starting material, 85 parts of a compound (Kpo, oi = 135 to 1q.2 °) which, according to analysis, was formed by the addition of 1 mole of the mercapto compound to 1 mole of the pentadiyne. Example 5 A mixture of 68 parts of 5-diethylamino-pentadün-i, 3.5o parts of tetrahydrofuran and 70 parts of methyl β-mercaptobutyrate is heated for some time to 50 ° and then to 70 to 80 °. The tetrahydrofuran and unconverted starting materials are then driven off in a water jet vacuum. The residue is distilled in a high vacuum. 75 parts of an amino thioether of the composition (# 14H2302NS (Kpo, o1 = 104 to 106 °, D1 ° = 1, oig8), which was formed by the addition of 1 mole of the mercapto compound to 1 mole of the diyne, are obtained.
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEC1709D DE902011C (en) | 1943-07-18 | 1943-07-18 | Process for the production of unsaturated compounds containing sulfur |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEC1709D DE902011C (en) | 1943-07-18 | 1943-07-18 | Process for the production of unsaturated compounds containing sulfur |
Publications (1)
Publication Number | Publication Date |
---|---|
DE902011C true DE902011C (en) | 1954-01-18 |
Family
ID=7012710
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DEC1709D Expired DE902011C (en) | 1943-07-18 | 1943-07-18 | Process for the production of unsaturated compounds containing sulfur |
Country Status (1)
Country | Link |
---|---|
DE (1) | DE902011C (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2119802A (en) * | 1933-12-20 | 1938-06-07 | Winthrop Chem Co Inc | Basically substituted enol and thienol ethers and esters |
-
1943
- 1943-07-18 DE DEC1709D patent/DE902011C/en not_active Expired
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2119802A (en) * | 1933-12-20 | 1938-06-07 | Winthrop Chem Co Inc | Basically substituted enol and thienol ethers and esters |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE1249867B (en) | Process for the production of carboxylic acids or carboxylic acid esters | |
DE2630086C3 (en) | Process for the preparation of pent-3-enoic acid and its alkyl esters | |
DE902011C (en) | Process for the production of unsaturated compounds containing sulfur | |
EP0025940B1 (en) | Process for the hydroxylation of olefinically unsaturated compounds | |
DE2314694B1 (en) | Process for the production of alpha, omega-dialdehydes | |
DE2202249C2 (en) | Process for the recovery of alpha-cedrene from the hydrocarbon fraction of cedarwood oil | |
EP0007076B1 (en) | Dihydrobisabolenes and dihydrobisabolol, their preparation and use as odorous substances | |
DE837998C (en) | Process for the preparation of aliphatic diketones | |
DE1768068C3 (en) | Process for the reductive removal of acidic organic derivatives of sulfuric acid from reaction mixtures with unsaturated terpene compounds | |
DE885846C (en) | Process for the preparation of alcohols of the acetylene series | |
DE1005954B (en) | Process for the production of polyene carboxylic acid esters or nitriles | |
DE862016C (en) | Process for the preparation of tetrahydropyran derivatives | |
DE870698C (en) | Process for the production of hydroquinones | |
DE1668646C (en) | Method for cleaning up benzyl alcohol | |
DE945146C (en) | Process for the production of elastic, high molecular weight alcohol-hydrocarbon mixtures | |
DE812072C (en) | Process for converting mercaptans or thioethers into carboxylic acid salts and carboxylic acids | |
DE1106316B (en) | Process for the production of organic polysulphides | |
DE933864C (en) | Process for the production of alcohols | |
DE835594C (en) | Process for the production of ª ‡, ª ‰ -dicarbonyl compounds and their acetals | |
DE1914038C3 (en) | Method for purifying methylglyoxal | |
DE877762C (en) | Process for the preparation of higher tetrahydrofurfurylalkylcarboxylic acids | |
DE1643985C3 (en) | S-Isopropyl ^ nitro-phenyl-dimethyl-carbinol and 3,5-diisopropyl-4-nitro-phenyldimethylcarbinol and processes for their preparation | |
DE874770C (en) | Process for the preparation of esters of ª-chlorobutyric acid | |
DE887502C (en) | Process for the production of unsaturated dicarboxylic acid anhydrides and the corresponding dicarboxylic acids | |
DE2166727A1 (en) | CYCLOPROPAN DERIVATIVES |